Published by : International Journal of Engineering Research & Technology (IJERT)

http://www.ijert.org ISSN: 2278-0181

Vol. 8 Issue 01, January-2019

Determination of Styrene Compatibility of

Polyester Resin and Influence of Raw
Materials - An overview
Jijo T George
Department of Research & Development
PolyKot Industries
Pala, Kerala, India

Abstract:-Styrene compatibility of orthophthalic polyester resin
and it’s variation with respect to nature and type of ingredients
was investigated. A useful method for manufacturing industry to
predict the styrene compatibility of resin at room temperature
was proposed. It will be useful to predict very common styrene
flotation problem during the storage time especially in
economical general purpose polyester resin.
Keywords:- Orthophthalic polyester resin, Raw material, Styrene
compatibility
INTRODUCTION
Unsaturated polyester resins (UPR) is widely used for a
variety of industrial and consumer applications. The
consumption can be split into two major categories of
applications viz., reinforced and non-reinforced. In reinforced
applications, resin and reinforcement (usually fibreglass) are
used together to produce a composite with improved physical
properties. Typical reinforced applications are boats, cars,
shower stalls, building panels, and corrosion- resistant tanks
and pipes. Non-fibre reinforced applications generally have a
mineral filler incorporated into the composite for property
modification. Some typical non-fibre reinforced applications
are sinks, bowling balls, and coatings. Polyester resin
composites are cost effective because they require minimal
setup costs and the physical properties can be tailored to
specific applications. Another advantage of polyester resin
composites is that it can be cured in a variety of ways without
altering the physical properties of the finished part.
Consequently, polyester resin composites compete favourably
in custom markets [2, 3].
Polyester resins are mainly classified into two classes
based on the chemical structure of the ingredients viz.,
orthophthalic and isophthalic resins. The orthophthalic resin is
used for general purpose applications of low cost without
compromising quality. Likewise, isophthalic resins preferred
for situations such as weather and chemical resistant
environment, better mechanical properties and higher heat
deflection temperature (HDT) [1,3].UPR is condensation
polymer formed by the reaction of diols and dicarboxylic acid
with water as the by-product normally. Ethylene glycol (EG),
diethylene glycol (DEG), propylene glycol (PG), methyl
propane diol (MPD), dipropylene glycol (DPG) and neopentyl
glycol (NPG) are well-known members in polyols family.
Phthalic anhydride (PA), isophthalic acid (IPA), terephthalic
acid (TPA), adipic acid (AA), maleic anhydride (MA) and
fumaric acid (FA) are normal industrial favourable members
in dicarboxylic acid molecules. For an unsaturated polyester
resin, it is necessary to add olefinic unsaturation in the
backbone to crosslink with a monomer such as styrene.
Usually maleic anhydride and fumaric acid provide the
unsaturation in the polymer chain. UPR with maleic/fumaric
and any polyols normally result a hard and brittle product of
poor mechanical properties.
To overcome these demerits, higher reactive aliphatic
unsaturated dicarboxylic acid/anhydride is partially replaced
with aromatic saturated dicarboxylic acid/anhydride (phthalic
anhydride, isophthalic acid, terephthalic acid etc.) and
aliphatic dicarboxylic acid (adipic acid) [1-3]. The nature and
the percentage of substitution in the main backbone define
properties of the end product. Partial substitution results in
decreased reactivity, reduced brittleness, lower exotherm
during the polymerization and increased mechanical
properties, toughness etc. An economical general purpose
resin, phthalic and maleic anhydrides are preferred.
Propylene glycol (PG) enhances maximum isomerisation of
lower reactive maleate to highly reactive fumarate and better
solubility in styrene monomer [1]. But a neat propylene glycol
batch is expensive due to the higher cost of PG when compare
with EG and DEG. In the UPR industry, cost of the product
has an important role to compete with other brands. There is a
possibility for the partial replacement of propylene glycol
(PG) with cheaper ethylene glycol (EG) and diethylene glycol
(DEG). DEG have seldom used because of the poor hydrolytic
stability and higher flexibility. Also, EG conjunction is
restricted due to the poor styrene compatibility. However,
many of the manufacturers extensively incorporate EG and
DEG in their formulation to reduce the cost. The main
drawback of this primary glycols conjunction is the styrene
separation during the storage time. Hence, it is very important
to find out the maximum limit of EG and DEG in the
formulation. This paper describes a useful method to measure
the exact styrene compatibility of economical orthophthalic
resin and influence of raw material in styrene compatibility
MATERIALS AND METHODS
All the raw materials procured were industrial grade with
purity of above 99.00%. Propylene glycol from Manali
petrochemical, Chennai, ethylene and diethylene glycol from
Reliance, adipic acid and maleic anhydride from JP Dyechem
Pvt Ltd, Mumbai, and phthalic anhydride from Aekyung
Petrochemical Co. Ltd, Korea.

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Experimental preparation of Orthophthalic Resin temperature to the room temperature as soon as possible to get
A four-necked five liters round bottom on a heating mantle UPR [12].
with a thermometer, condenser, Nitrogen stream flow and a
RESULTS AND DISCUSSIONS
mechanical agitator was designed as a glass reactor for the
preparation of UPRs. Mol % composition various raw
Styrene Compatibility of the UPR
materials to prepare UPRs are given the following Table: 1.
The solid percentage of a UPR is tried to reduce by careful
addition of styrene monomer, at a particular solid level the
Table 1. Experiments based on different raw materials at
resin becomes cloudy at room temperature. The solid
different molar ratios
percentage at this cloudy state is defined as styrene cloud
Mol in % point (SCP). The solid percentage at which styrene starts to
No
Ref PA AA PG EG DEG MA separate and reach as a constant safe solid level which is free
from any further separation is considered as an optimum solid
1 UPR 1 23.4 - 31.9 14.3 7.0 23.4 percentage (OS%)”. If the manufacturer keeps the solid level
2 UPR 2 23.8 - 13.1 28.8 10.5 23.8 in their resin as the exact OS %, will not face any separation
3 UPR 3 31.0 - 13.1 32.2 7.0 16.7
problem during the shelf life period. Styrene compatibility of
the UPR was defined by the parameters styrene cloud point
4 UPR 4 31.0 - 31.5 13.8 7.0 16.7 (SCP) and Optimum Solid Percentage (OS %) and was
5 UPR 5 - 23.8 - - 52.4 23.8 obtained as follows,
Styrene at 25+ 1 °C forms a burette slowly and gradually
6 UPR 6* 23.4 - 31.9 14.3 7.0 23.4
added to 250 ml beaker contains 25 to 50 g of resin with a
*same formula of UPR 1, but the maximum batch temperature
known % of solid. Stir well and check for the change in
was limited as 199°C. [PA-Phthalic anhydride; AA-Adipic
transparency or cloudiness after every 1 ml of addition.
acid; PG-Propylene glycol; EG-Ethylene glycol; DEG-
Continue the styrene addition until the solution becomes
Diethylene glycol; and MA-Maleic anhydride
cloudy.
Styrene Cloud Point, SCP =
Actual Solid in Sample, g × 100

Wt. of Resin, g + (Amount of Styrene, ml × 0.910) g

(1)

The styrene cloud point value of deferent experiments are

given in the following Table: 2
At this clouding point or extra 1-2 ml addition of styrene can
observe small micro ball like suspended solid resin particle-
rich solution in the beaker at a closer observation in front of a
light source.

Determination of Optimum Solid Percentage (OS %)

The solid content of resin was reduced to its SCP by adding
extra styrene monomer and fill up to the mark of 100 ml in a
measuring cylinder of accuracy of 0.1 ml. The separation of
styrene on the top of the mixture was gradually checked until
the separation got stabilized (3 days to 1 week may it will take
Figure: 1, Glass reactor set up for UPR Processing [1) Total condenser, 2) at room temperature 26 ± 2 °C). The final amount of separated
Partial condenser, 3) Motor with a stirrer, 4) Nitrogen, 5) water inlet, 6) styrene and the OS% were calculated as follows;
water outlet, 7) Thermometer and 8) Heating mantle Optimum Solid Percentage (OS%) =
SCP × (A1 x d1)
The experiment was conducted in a nitrogen stream and the
(A1 × d1) (A1 × 0.910) (2)
temperature was gradually increased to 100 °C and kept
where A1 and d1 are the amounts and the density of mixture
constant. (The experimental set up shown in the Figure: 1). As
was taken respectively, A2 is the amount of styrene separated
a consequence of exothermic reaction by the ring opening of
of density 0.910, and SCP is Styrene Cloud Point.
maleic anhydride, the temperature is raised up to the
The calculated OS % results of different UPR are given in
maximum. Cook the batch for an hour at 180 °C when the
following table 3.
exothermic reaction becomes stabilised. Heat the solution up
to 215-220 °C and maintain until the acid value of about 30
mg KOH/g, then cool it to 185 °C and add mono-t-butyl
hydroquinone to prevent pre-mature polymerisation. Further
cool to 150 °C and blend with enough cold styrene so as to get
60 % solid content in the final solution then reduce blenders’

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Table 2: Styrene Cloud Point, (SCP) of different resins Table 4: Styrene cloud point at different temperatures
prepared as given in Table: 1 No Ref SCP at 25° C SCP at 45° C
1 UPR 1 13.9 <5

Ref Mol % 2 UPR 2 52.7 37.2

No
PA AA PG EG DEG MA SCP 3 UPR 3 49.6 31.0

1 UPR 1 23.4 - 31.9 14.3 7.0 23.4 13.9 4 UPR 6 35.5 20.7

2 UPR 2 23.8 - 13.1 28.8 10.5 23.8 52.7 5 UPR 7 41.2 30.1

3 UPR 3 31.0 - 13.1 32.2 7.0 16.7 49.6 b) Process condition of resin preparation:
4 UPR 4 31.0 - 31.5 13.8 7.0 16.7 <5 In general, polyester resins are processing in a controlled
5 UPR 5 - 23.8 - - 52.4 23.8 16.9
manner as stated early in this paper. The batch cooked at
higher temperature of 215 to 220°C and targeting for an acid
6 UPR 6 23.4 - 31.9 14.3 7.0 23.4 35.5 value of approximately 30 mg KOH/g [1,10]. All resin
PA-Phthalic anhydride; AA-Adipic acid; PG-Propylene glycol; prepared in this invention is followed the said statement
EG-Ethylene glycol; DEG-Diethylene glycol; and MA-Maleic except UPR 6. In the case of UPR 6, the maximum
anhydride temperature of the reaction limited as 199°C and blending
started at an acid value at 55mg KOH/g. Consider the SCP and
Table 3: Optimum Solid Percentage (OS %) of the UPRs OS% result of UPR1 and UPR 6 in the Table: 3. The UPR 1
No Ref SCP OS% which is followed the exact process procedure show SCP and
OS% as 13.9. UPR 6 with lower process temperature and
1 UPR 1 13.9 13.9
higher acid value exhibit lesser styrene compatibility than
2 UPR 2 52.7 54.9 UPR 1 and the SCP & OS% as 35.5% and 41.1 % respectively.
3 UPR 3 49.6 52.2
These two experiments are same in formulation wise but their
process condition was different. Now experimentally it is
4 UPR 6 35.5 41.1 cleared that, process condition can also affect the styrene
5 UPR 7* 41.2 47.2 compatibility in the same formulation. The change in styrene
*UPR 7 is a commercial UPR – Qupol 142 UO (a known cloud point and optimum solid level by the process condition
brand of Sulaiman Al-Qudaibi Co. for Resin production, is permanent and it will not deviate like the influence of room
Kuwait) and material temperature during the SCP experiment.

Non-separation tendency of styrene from SCP CONCLUSION

If go lower SCP, say below 20%, the separation tendency of
styrene minimized or never happen and at this moment OS%
becomes equal to SCP and it has not any particular application
or any logical value in the industrial segment. This is because;
the industrial UPR’s solid level usually starts at 40 %. The
compatibility issue and separation tendency are more when
the SCP above at 40; hence it has an important role in the UPR
industry.
Apart from the raw materials and it’s different compositions,
there are two more factors which make an influence in the
styrene cloud point and hence optimum solid percentage also,
a) The temperature during the SCP experiment:
It is found that there is a significant change in lowering the
SCP of UPR 1, 2, 3, 6 and 7 when the SCP experiment
conducted at room temperature 45° C. But this is a temporary
observation. The solution becomes cloudy and start to separate
styrene when it returns to room temperature 25° C. So the
influence of the room and material temperature on the SCP is
temporary during the experiment that shown in Table 4,
Methods to determine the styrene compatibility of polyester
resin and influence of raw material and its percentage in the
compatibility is presented. The styrene compatibility is mainly
affected by the change in the percentage of secondary diol –
Propylene glycol. Also, Phthalic anhydride has a role to
increase in the compatibility but the effect is minor like
diethylene glycol. A huge dramatic variation we can observe
by playing with PG to EG ratio. The styrene separation from
the clouding point can’t observe at lower SCP say below 20,
but as per industrial concept the solid level starts from 40 %
hence can ignore the importance of styrene cloud point behind
20%. These experiments are prepared in the laboratory to
explain the methods to determine the styrene compatibility
only. Because of the process condition, volume and other
factors, the mentioned formulations may exhibit different
values in bulk commercial batches.
The simplest experimental methods to determine SCP and
OS% described in this invention is very useful to identify the
styrene compatibility of UPR and predict the styrene
separation problem happen or not. This invention is also an
index for the process history of the resin batch produced. We
confidently believe that this invention is acceptable for UPR
industry because of the above-said application fields.

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ACKNOWLEDGEMENT

The author would like to acknowledge, Dr. John Prakash,

Dept. of Chemistry, Central University, Tamil Nadu, India

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